Process for breaking petroleum emulsions



United States Patent PROCESS FOR BREAKING PETROLEUM EMULSIONS Serial No. 321,040

32 Claims. (Cl. 252-9341) Ne Dr ppl a No em er .17, i9 2,

This invention relates to a process for breaking petroleum emulsions of the water-in-oil type and is characterized by subjecting such an emulsion to the action of a demulsifier, including certain acidic fractional esters which are disclosed in my co-pending application S. N. 321,035, filed November 17, 1952, and which are derived by esteri-. fying an oxyalkylated amine-modified phenol-aldehyde resin condensate with a polycarboxy acid.

Ignoring the preparation of the phenol-aldehyde resin per se the remainder of the reactions fall into three classes: (1) condensation, (2) oxyalkylation, and (3) esterificas tion.

The acidic fractional esters obtained in the manner herein described have utility for various purposes and particularly for the resolution of petroleum emulsions of the water-in-oil type. In this connection it should be noted that the polyhydroxylated reactant or reaction mixture may be obtained by combining a comparatively large proportion of the alkylene oxide, particularly propylene oxide, or a combination of propylene oxide and ethylene oxide, with a comparatively small proportion of the resin condensate. In some instances the ratio has been as high as fifty-to-one, i. e., the ultimate product of oxyalkylation contained about 2% of resin condensate and approxi: mately 98% alkylene oxide. This was, of course, prior to the esterification step. V

Momen r y o g h fina s ep of es rifi e en this invention i a o m ted a pe a far s t e e actants are concerned which, in turn, are subjected to oxyalkylation and then esterification, are as previously o e ce n a n fie h rmopl ic Phenolaldehyde resins. Subsequent description in regard to the am e-modifi d resins mpl e s ar e i eh ea ith the text as it appears in certain co-pending applications, to r a t 2 4 e y 9 9. and Seria No. 01,301 led u y3 /19 2- or purp se o si ie y the nve i p y from a s ah iw h o the resin condensate involved, may be exemplified by an idealized formula as follows:

R R v n in which R represents an aliphatic hydrocarbon substituent generally having four and not over 18 carbon atoms but most preferably not over 14 carbon atoms, and n generally is a small whole number varying from 1 to 4.. In the resin structure it is shown as being derived from f r a e de l ho h b iousl oth ald h de a eq al y s e yhe m es due n he abo e stru ue is d r rom e er a. bs utetl ida ql n or a substituted tetrahydropyri nidine as previously specie i d and may be n ica d thu in which represents a reactive secondary amino group and two occurrences of R represent the remainder of the molecule.

Stated another way, what has been depicted in the above formula is an over-simplification as far as the ring compound is concerned which is obvious by reference to a more elaborate formula depicting the actual structure of typical members of the group, such as 2-rnethyl,1hoganeoyla-rninoetl yla ninoethylimidazoline 2-1;eptadecyl,l-rnethylaminoethyl tetrahydropyrimidine Th intredu tie o t o uc n p d d a s n ompara ely sma res n l cul for s a c on ha ng? to Pheno i n e as sp i d te t modes nla number f way n the fi plac a basic troge stem, at eeu se, add a hy phile e t; n h s eeh Pl e depen ing he he t t e di f ther ma be a equn e halane ydrop eh e c o ehe i wh h th hyehe he e ct more n counterw lanc he hy re i e ei ee f he nit o n atom- Finally, in such cases where R contains one or more xy ato s, anoth r et eet is intr du p ti u a y anothe h rephi ef ec s In su h ns n where there a y y ps present ne dless to y e e is s r her hy r h l ffe introdu e Refe r n ain o h res s a suc it is th not n ha combination eit e r s hc s or et e wi e, ve een, prepared from phenols, aldehydes, and reactive amines pe ii ul r m o-amin Ce h ne ien e no or othe a e e n p pared from phenols, aldehydes, and reactive amines, particularly amines having secondary amino groups. Genra y s eak n ueh mat ria have fallen n th e l ses; he rst repres nt h ne us e en derived from phenols as such; the second class represents esins hieh a e us a ly insoluble a d sed tor the pur- Pese fe whi h o din y resins, pa ieula v h m ett es n are adapt d he th r l s ep nt es s which are soluble as initially prepared but are not heatstable, i. e., they are heat-convertible, which means they are not particularly suited as raw materials for subsequent chemical reaction which requires temperatures above the boiling point of water or thereabouts.

As to the preparation of the first class, i. e., non-resinous materials obtained from phenols, aldehydes and amines, particularly secondary amines, see United States Patents Nos. 2,218,739 dated October 22, 1940, to Bruson; 2,033,092 dated March 3, 1936, to Bruson; and 2,036,916 dated April 7, 193 6, to Bruson.

As to a procedure by which a resin is produced as such involving all three reactants and generally resulting in an insoluble resin, or in any event, a resin which becomes insoluble in presence of added formaldehyde or the like, see United States Patents Nos. 2,341,907, dated February 15, 1944, to Cheetham et al.; 2,122,433, dated July 5, 1938, to Meigs; 2,168,335, dated August 8, 1939, to Heckert; 2,098,869, dated November 9, 1937, to Harmon et al.; and 2,211,960, dated August 20, 1940, to Meigs.

A third class of material which approaches the closest to the herein-described derivatives or resinous amino derivatives is described in U. S. Patent No. 2,031,557, dated February 18, 1936, to Bruson.

The resins employed as raw materials in the instant procedure are characterized by the presence of an aliphatic radical in the ortho or para position, i. e., the phenols themselves are difunctional phenols. This is a differentiation from the resins described in the aforementioned Bruson patent, No. 2,031,557, insofar that said patent discloses suitable resins obtained from metasubstituted phenols, hydroxybenzene, resorcinol, p,p'(dihydroxydiphenyl)dimethylmethane, and the like, all of which have at least three points of reaction per phenolic nuclei and as a result can yield resins which may be at least incipiently cross-linked even though they are apparently still soluble in oxygenated organic solvents or else are heat-reactive insofar that they may approach insolubility or become insoluble due to the effect of heat, or added formaldehyde, or both.

The resins herein employed contain only two terminal groups which are reactive to formaldehyde, i. e., they are difunctional from the standpoint of methylol-forming reactions. As is well known, although one may start with difunctional phenols, and depending on the procedure employed, one may obtain cross-linking which indicates that one or more of the phenolic nuclei have been converted from a difunctional radical to a trifunctional radical, or in terms of the resin, the molecule as a whole has a methylol-forming reactivity greater than 2. Such shift can take place after the resin has been formed or during resin formation. Briefly, an example is simply where an alkyl radical, such as methyl, ethyl, propyl, butyl, or the like, shifts from an ortho position to a meta position, or from a para position to a meta position. For instance, in the case of phenol-aldehyde varnish resins, one can prepare at least some in which the resins, instead of having only two points of reaction can have three, and possibly more points of reaction, with formaldehyde, or any other reactant which tends to form a methylol or substituted methylol group.

Apparently there is no similar limitation in regard to the resins employed in the aforementioned Bruson Patent 2,031,557, for the reason that one may prepare suitable resins from phenols of the kind already specified which invariably and inevitably would yield a resin having a functionality greater than two in the ultimate resin molecule.

The resins herein employed are soluble in a nonoxygenated hydrocarbon solvent, such as benzene or xylene. As pointed out in the aforementioned Bruson Patent 2,031,557, one of the objectives is to convert the phenol-aldehyde resins employed as raw materials in such a way as to render them hydrocarbon soluble, i. e., soluble in benzene. The original resins of U. S. Patent 2,031,5 57

are selected on the basis of solubility in an oxygenated inert organic solvent, such as alcohol or dioxane. It is immaterial whether the resins here employed are soluble in dioxane or alcohol, but they must be soluble in benzene.

The resins herein employed as raw materials must be comparatively low molal products having on the average 3 to 6 nuclei per resin molecule. The resins employed in the aforementioned U. S. Patent No. 2,031,557, apparently need not meet any such limitations.

The condensation products here obtained, whether in the form of the free base or the salt, do'not go over to the insoluble stage on heating. This apparently is not true of the materials described in aforementioned Bruson Patent 2,031,557 and apparently one of the objectives with which the invention is concerned, is to obtain a heat-convertible condensation product. The condensation product obtained according to the present invention is heat stable and, in fact, one of its outstanding qualities is that it can be subjected to oxyalkylation, particularly oxyethylation or oxypropylation, under conventional conditions, i. e., presence of an alkaline catalyst, for example, but in any event at a temperature above C. without becoming an insoluble mass.

What has been said previously in regard to heat stability, particularly when employed as a reactant for preparation of derivatives, is still important from the standpoint of manufacture of the condensation products themselves insofar that in the condensation process employed in preparing the compounds described subsequently in detail, there is no objection to the employing of a temperature above the boiling point of water. As a matter of fact, all the examples included subsequently employ temperatures going up to to C. If one were using resins of the kind describedin U. S. Patent No. 2,031,557 it appears desirable and perhaps absolutely necessary that the temperature be kept relatively low, for instance, between 20 C. and 100 C. and more specifically at a temperature of 80 to 90 C. There is no such limitation in the condensation procedure herein described for reasons which are obvious in light of what has been said previously.

What is said above deserves further amplification at this point for the reason that it may shorten what is said subsequently in regard to the production of the herein described condensation products. As pointed out in the instant invention the resin selected is xylene or benzene soluble, which differentiates the resins from those employed in the aforementioned Bruson Patent No. 2,031,- 557. Since formaldehyde generally is employed economically in an aqueous phase (30% to 40% solution, for example) it is necessary to have manufacturing procedure which will allow reactions to take place at the interface of the two immiscible liquids, to wit, the formaldehyde solution and the resin solution, on the assumption that generally the amine will dissolve in one phase or the other. Although reactions of the kind herein described will begin at least at comparatively low temperatures, for instance, 30 C., 40 C., or 50 (1, yet the reaction does not go to completion except by the use of the higher temperatures. The use of higher temperatures means, of course, that the condensation product obtained at the end of the reaction must not be heat-reactive. Of course, one can add an oxygenated solvent such as alcohol, dioxane, various ethers of glycols, or the like, and produce a homogeneous phase. If this latter procedure is employed in preparing the herein described condensations it is purely a matter of convenience, but whether it is or not, ultimately the temperature must still pass within thezone indicated elsewhere, i. e., somewhere above the boiling point of water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims, to the procedure employed in the process is not intended to limit the method or order in which the reactants are added, commingled or reacted. The procedure has been reffit f fed to as a condensation process for obvious reasons. As pointed out elsewhere it my preference to dissolve the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However, all three reactants can be added in any order. I am inclined to believe that in the presence of a basic catalyst, such as the amine employed, that the formaldehyde produces methylol groups attached to the phenolic nuclei which, in turn, react with the amine. It would be immaterial, of course, if the formaldehyde reacted with the amine so as to introduce a methylol group attached to nitrogen which, in turn, would react with the resin molecule. Also, it would be immaterial if both types of compounds were formed which reacted with each other with the evolution 1 of a. mole of formaldehyde available for further reaction. Furthermore, a reaction could take place in which three different molecules are simultaneously involved although, for theoretical reasons, that is. less likely. What is said herein in this respect is simply by way of explanation to avoid any limitation in regard to the appended claims.

Again it isv to be emphasized that at the end of the oxyalkylation step an esterification step follows.

Whether the amines herein employed are hydroxylated or not, it is obvious the amine-modified resin is susceptible. to oxyalkylation by virtue of the phenolic hydroxyl radicals. Referring to. the idealized formula which appeared previously it is obvious the oxyalkylated derivatives, or at least a substantial portion of time, could be indicated in the following manner:

R R i n R in which RO is the radical of alkylene oxide, such as the ethoxy, propoxy or similar radicals derived from ethylene oxide, propylene oxide, glycide or the like, and n is a number varying from 1 to 50, with the proviso that one ned not oxyalkylate all the available phenolic hydroxyl radicals. In other words, one need only convert two phenolic hydroxyl radicals per resin molecule. Stated another Way, n can be zero as well as a Whole number subject to what has been said immediately preceding, all of which will be considered in greater detail subsequently.

Actually what has been. said previously is not as, complete an idealized presentation as is desirable due to another factor involved. The factor is this; since the substituted imidazoline or substituted tetrahydropy-rimidine may have a hydroxyl. group or a tertiary amine group which is not susceptible to oxyethylation, it may also have more than one secondary group and thus the cyclic amine residue per se may be susceptible to oxyalkylation tion there are phenolic hydroxyl groups available which are readily susceptible to oxyalkylation and also there may be present hydroxyl groups as part of the cyclic amine residue. If one assumes for the moment the cyclic amine residue contains at least one or possibly two points olf oxyalkylation susceptibility then the condensate, ignoring any attempt to show an actual ring, can be depicted more satisfactorily by first referring to the resin condensate and then to the oxyalkylated derivative.

R R n in which the characters have their previous significance, and n" is the integer O or a small whole number, with the proviso that in each terminal amino radical there must be at least one hydroxyl group.

Thus one can show and with all propriety assume that to som e en ev n at he in t a s age, xyalky a i n does take place in reactions of the kind described, not only at the phenolic hydroxyl but also at the. hydroxyls which are part of the amino radical. This can be depiCted in the following manner:

in which for simplicity the formula just shown has been limited to the specific instance where there is one oxyalkylation-susceptible hydroxyl radical present as part of the cyclic amine residue.

Assuming, however, the cyclic residue does not have a labile hydrogen attached to oxygen but does have a labile hydrogen attached to nitrogen, then the condensate derivative may be indicated thus:

Similarly, going to the oxyalkylated product and following through the assumption just made in regard to the resin condensate the idealized formula may be presented thus:

The characters in the two previous formulas have the same significance as previously and no further elaboration is required.

As stated, in the above formulas R"O is the radical of an alkylene oxide such as ethoxy, propoxy, or similar radicals derived from ethylene oxide, propylene oxide, glycide or the like, and n is a number varying from 1 to 60, with the proviso that one need not oxyalkylate all the available phenolic hydroxyl radicals or all the available amino hydrogen atoms to the extent they are present. In other words, one need convert only two labile hydrogen radicals per condensate. It is immaterial whether the labile hydrogen atoms be attached to oxygen or nitrogen. As far as the use of the herein described products goes for the purpose of resolving petroleum emulsions of the water-in-oil type, I prefer to use those which have sufficienthydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368 dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity. In the present instance the esters of the various condensation products may not necessarily be xylene-soluble although they are xylene-soluble in a large number of instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalentchernical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reasonthat there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

Reference is again made to U. S. Patent 2,499,368 dated March 7, 1950, to De Groote and Keiser. In said immediately aforementioned patent the following test appears:

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called sub-surface-active stage. The surface-active properties are readily demonstrated by producing a xylene-water emulsion. A suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. Such 50-50 solution is then mixed with 1-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably suflicient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions so produced are usually xylene-in-water emulsions (oil-in-water type) particularly when the amount of distilled water used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At times, particularly in the lowest stage of oxyalkylation, one may obtain a waterin-xylene emulsion (water-in-oil type) which is apt to reverse on more vigorous shaking and further dilution with Water.

If in doubt as to this property, comparison with a resin obtained from para-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1 formaldehyde) using an acid catalyst and then followed by oxyalkylation using 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful. Such resin prior to oxyalkylation has a molecular weight indicating about 4 /2 units per resin molecule. Such resin, when diluted with an equal weight of xylene, will serve to illustrate the above emulsification test.

In a few instances, the resin may not be sufficiently soluble in xylene alone but may require the addition of some ethylene glycol diethylether as described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalent of xylene for the purpose of this test.

In many cases, thcre'is no doubt as'to the presence or absence of hydrophile or surface-active characteristics in the products used in accordance with this invention. They dissolve or disperse in water; and such dispersions foam readily. With borderline cases, i. e., those which show only incipent hydrophile or surface-active property (subsurface-activity) tests for emulsifying properties or selfdispersibility areuseful. The fact that a reagent is capable of. producing a dispersion in water is proof that it is distincty hydrophile. In doubtful cases, comparison can be made with the butylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus.

The presence of xylene or an equivalent water-insoluble solvent may mask the point at which a solvent-free product on mere dilution in a test tube exhibits self-emulsification. For this reason, if it is desirable to determine the approximate point where self-emulsification begins, then it is better to eliminate the xylene .or equivalent from a small portion of the reaction mixture and test such portion. In some cases, such xylene-free resultant may show initial or incipient hydrophile properties, whereas in presence of xylene such properties would not be noted. In other cases, the first objective indication of hydrophile properties may be the capacity of the material to emulsify an insoluble solvent such as xylene. It is to be emphasized that hydrophile properties herein referred to are such as those exhibited by incipient self-emulsification or the presence of emulsifying properties and go through the range of homogeneous dispersibility or admixture with water even in presence of added water-insoluble solvent and minor proportions of common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used to determine ranges of surface-activity and that such emulsification tests employ a xylene solution. Stated another way, it is really immaterial whether a xylene solution produces a sol or whether it merely produces an emulsion.

Having described the invention briefly and not necessarily in its most complete aspect, the text immediately following will be a more complete description with specific reference to reagents and the method of manufacture.

For convenience the subsequent text will be divided into six parts:

Part 1 is concerned with the general structure of the amine-modified resin condensates and also the resin itself, which is used as a raw material;

Part 2 is concerned with appropriate cyclic amidines selected from the class consisting of substituted imida-' zolines and substituted tetrahydropyrimidines in which there is present atleast one basic, secondary amino radical and characterized by freedom from any primary amino radical;

Part 3 is concerned with the condensation reactions involving the resin, the amine, and formaldehyde to produce the specific products or compounds;

Part 4 is concerned with the oxyalkylation of the products described in Part 3, preceding;

Part 5 is concerned with the conversion of the polyhydroxylated compounds or reaction mixtures described in Part 4 preceding, into acidic fractional esters by means of polycarboxy acids; and

. Part6 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the acidic fractional esters previously described.

In the subsequent text, Parts 1, 2 and 3 appear in substantially the same form as the text of the aforementionedco-pending application, Serial No. 288,746, filed May l9, 1952, and also in aforementioned co-pending application, Serial No. 301,807, filed July 30, 1952. Part 4 is substantially the same as Part 4 as it appears in the last mentioned co-pending application. The text is so presented for both purpose of convenience and comparison. Similarly, Part 5 is substantially the same 9 as it appears in aforementioned co-pending application, Serial No. 321,035, filed November 17, 1952-.

PART 1 on [on on H n C C- OH H n R n R In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., it varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol,

for instance para-phenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethylglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368 dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation-susceptible, fusible, nonoxygenated-organic solvent-soluble, waterinsoluble, low-stage phenol-aldehyde resins having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of tri-functional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at H C H 10 least 4 carbon atoms and not more than 24 carbon atoms, and substituted in the 2,4,6 position.

If one selected a resin of the kind just describedpreviously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant productmight be illustrated thus:

The basic amine may be designated thus:

R) a structure such as a substituted imidazoline or substituted tetrahydropyrirnidine such as the following:

N-CH2 then one becomes involved in added difiiculties in presenting an overall picture. Thus, for sake of simplicity the ring compound having the reactive secondary amino group will be depicted as R! subject to the limitation and explanation previously noted.

In conducting reactions of this kind one does not necessarily obtain a hundred per cent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formula:

thus:

OH I OH RIII R n R in which R' is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is Well known. See previously mentioned U. S. Patent 2,499,363. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although I have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few lOths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found no reason for using other than those which are lowest in price and most readily availiable commercially. For purposes of convenience suitable resins are characterized in the following table:

TABLE I Mol. wt. Ex Position R derived R n of resin No. of R f. om m 01 e cule 1a...- Phenyl Para. Formaldehyde. 3 5 992. 5 2a Tertiary butyl.. do d 3. S82. 5 311.... Secondary butyL. 3. 5 882. 5 4a-. Cyclohexyl 3. 5 1, 025. 5 5a...- Tertiary amyl 3. 5 959. 5 6a.-.. Mixed secondary 3. 5 805. 5

and tertiary amyl. Propyl 3. 5 805. Tertiary hexyl 3. 5 1, 036. t 3. 5 1, 190. 3. 5 1, 267. Decyl 3. 5 1,344. Dodeeyl do 3. 5 1,498. Tertiary butyl. Aeetaldehyde 3. 5 945. 14a-.- Tertiary amyl... d0 3. 5 1, 022. d0 3. 5 1, 330. Butyraldeliyde. 3. 5 1, 071. ..do 3.6 1, 148. do 3. 5 1, 456. Propionalde- 3. 5 1, 008.

12 PART 2 The expression cyclic amidines is employed in its usual sense to indicate ring compounds in which there are present either 5 members or 6 members, and having 2 nitrogen atoms separated by a single carbon atom supplemented by either two additional carbon atoms or three additional carbon atoms completing the ring. All the carbon atoms may be substituted. The nitrogen atom of the ringinvolving two monovalent linkages may be substituted. Needless to say, these compounds include members in whichthe substituents also may have one or more nitrogen atoms, either in the form of amino nitrogen atoms or in the form of acylated nitrogen atoms.

These cyclic amidines are sometimes characterized as being substituted imidazolines and tetrahydropyrimidines in which the two-position carbon of the ring is generally bonded to a hydrocarbon radical orcomparable radical derived from an acid, such as a low molal fatty acid, a high molal fatty acid, or comparable acids such as polycarboxy acids.

Cyclic amidines obtained from oxidizedwax acids are described in detail in co-pending Blair application,

where R is a member of the class consisting of hydrocarbon radicals having up to approximately 30 carbon atoms and includes hydroxylated hydrocarbon radicals and also hydrocarbon radicals in which the carbon atom chain is interrupted by oxygen; n is the numeral 2 to 3, D is a member of the class consisting of hydrogen and organic radicals containing less than 25 carbon atoms, composed of the elements from the group consisting of C, N, O and H, and B is a member of the group consisting of hydrogen and hydrocarbon radicals containing less than 7 carbon atoms, with the proviso that at least threeoccurrences of B are hydrogen. The preparation of an imidazoline substituted in the two-position by lower aliphatic hydrocarbon radicals is described in the literature and is readily carried out by reaction between a monocarboxylic acid or ester or amide and a diamine or polyamine, containing at least one primary amino group, and at least one secondary amino group or a second primary amino group separated from the first primary amino group by two carbon atoms.

Examples of suitable polyamines which can be employed as, reactants to form basic nitrogen-containing compounds of the present invention include polyalkylene polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and higher polyethylene polyamines, and also including 1,2- diaminopropane, N-ethylethylenediamine, N,N-dibutyldiethylenetriamine, 1,2-diaminobutane, hydroxycthylethylenediamine, 1,2-propylenetriamine, and the like.

For details'of the preparation of imidazolines substituted in the 2-position from amines of this type, see the following U. S. patents: U. S. No. 1,999,989 dated April 30, 1935, Max Bockmuhl et al.; U. S. No. 2,155,877 dated April 25, 1939, Edmund Waldmann et al.; and U. S. No. 2,155,878 dated April 25, 1939, Edmund Waldmann et al., also see Chem. Rev., 32, 47 (43). Equally suitable for use in preparing compounds of myin-vention and for the preparation of tetrahydropyriniidines substituted in the 2-position are the polyamines containing at least one primary amino group and at least one secondary amino group, or another primary amino group separated from the first primary amino group by three carbon atoms. This reaction is generally carried out by heating the reactants to a temperature of 230 C. or higher, usually within the range of 250 C. to 300 C., at which temperatures Water is evolved and ring closure is effected. For details of the preparation of tetrahydropyrimidines, see German Patent No. 700,371 dated December 18, 1940, to Edmund Waldmann and August Chwala; German Patent No. 701,322 dated January 14, 1941, to Karl Kiescher, Ernst Erech and Willi Klarer; and U. S. Patent No. 2,194,419 dated March 19, 1940, to August Chwala.

Examples of amines suitable for this synthesis include 1,3-propylenediamine, trimethylenediamine, l,3-diaminobutane, 2,4 diaminopentane, M ethyl trimethylenediamine, N-aminoethyltrimethylene diamine, aminopropyl stearylamine, tripropylenetramine, tetrapropylenepentamine,.high boiling polyarnines prepared by the condensation of 1,3-propylene dichloride with ammonia, and similar diamines or polyamines in which there occurs at least one primary amino group separated from another primary or secondary amino group by three carbon atoms.

Similarly, the same class of materials are included as initial reactants in co-pending Smith application, Serial No. 281,645, filed April 10, 1952, now Patent No. 2,713,559 dated July 19,1955. Said application in essence states that the cyclic compounds employed may be derived from either polyamines in which the nitrogen atoms are separated by an ethylene radical or by a trimethylene radical. Reference to a propylene radical means a methyl substituted ethylene radical, i. e., having only 2 carbon atoms between nitrogen atoms. From a practical standpoint, as will be explained hereinafter, the polyethylene imidazolines are most readily available and most economical for use, 'Ihus, broadly speaking, using the same terminology as said Smith application, Serial No. 281,645, the present'invention is concerned with a condensation reaction, in which one class of reactants are substituted ring compounds consisting of in which R is a divalent alkylene radical selected from the class consisting of and in which D' represents a divalent, non-amino, organic radical containing less than carbon atoms, composed of elements from the group consisting of C, H, O, and n; Y represents a divalent, organic radical containing less than 25 carbon atoms, composed of elements from the group consisting of C, H, O, and N, and containing at least one amino group, and R is a member of the class consisting of hydrogen, aliphatic hydrocarbon radicals, hydroxylated aliphatic hydr0carbon radicals, cycloaliphatic hydrocarbon radicals, and hydroxylated cycloaliphatic hydrocarbon radicals; R" is a member of the class consisting of hydrogen, aliphatic radicals and cycloaliphatic radicals, with the proviso that in the occurrence of the radicals R and R" there be present at least one group of 8 to 32 uninterrupted 14 carbon atoms. In the present instance, however, there is no limitation in regard to the radicals R and R".

What has been said previously in regard to the two above copending applications as far as substituted imidazolines are concerned is substantially the same as appears in Blair and Gross Reissue Patent No. 23,227, reissued May 9, 1950, and Monson Patent No. 2,589,198 dated April 11, 1952.

As to the six-membered ring compounds generally re ferred to as substituted pyrimidines, and more particularly as substituted tetrahydropyrimidines, see U. S. Patent No. 2,534,828 dated December 19, 1950, to Mitchell et al. With the modification as far as the instant application goes, the hydrocarbon group R may have the same variation as when it is part of the five-membered ring previously referred to and is not limited to an alkyl group having at least 10 carbon atoms as in the instance of the aforementioned U. S. Patent No. 2,534,828.

For the purpose of the present invention there is selected from the broad case of compounds previously described such members as meet the following limitations: (a) Have present at least one basic secondary amino radical; and (b) be free from primary amino groups and especially basic primary amino groups. Such compounds may have two-ring membered radicals present instead of one ring-membered radical and may or many not have present a tertiary amine radical or a hydroxyl radical, such as a hydroxy alkyl radical. A large number of compounds have been described in the literature meeting the above specifications, of which quite a few appear in the aforementioned issued U. S. patents. Examples selected from the patents include the following:

CnHznC 2-undecyllmidazoline N H2 C H35. 0

NC H:

Z-heptadecylimidazoline %NCH2 2-oleylimidazoline N-CHz aHo.NH.C mHas 1-dodecylaminopropyllmidazoline IHLNH. C ZHQO C 11.0 "H35 1- stearoyloxyethyl) aminoethylimidazoline N-orn (8) NCH1 v C2H4.NH.C2H4NHOC.C11H35 l-steararnidoethylaminoethylimidazoline N-CH2 H.C\ (9) C2H4.N.C2H4-NHOC.CH3

izHzs 1 (N-dodecy1) -acetamidoethylaminoethylimidazoline N-CH-OH; C17Hss-C (10) 2-heptadecyl,4,5-dimethylimidazoline N-C H7 6HmNH. C tzxHas l-dodecylaminohexylimidazoline NCH zHtNHC zHrN 4-methyl,2-dodecyl,1-1netl1ylaminoethylaminoethyl tetrahydropyrimidine As has been pointed out previously, the reactants herein employed may have two substituted imidazoline rings or two substituted tetrahydropyrimidine rings. Such compounds are illustrated by the following formula Such compounds can be derived, of course, from triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and higher homologues. The substituen-ts may vary depending on the source of the hydrocarbon radical, such as the lower fatty acids and higher fatty acids, a resin acid, naphthenic acid, or thelike. The group introduced may or may not contain a hydroxyl radical as in the case of hydroxyacetic acid, acetic acid, ricinoleic acid, oleic acid, etc. 7

One advantage of a two-ring compound resides in the fact that primary amino groups which constitute the terminal radicals of the parent polyamine, whether a'polyethylene amine or polypropylene amine, are converted so as to eliminate the presence of such primary amino radicals. Thus, the two-membered ring compound meets the previous specification in regard to the nitrogen-contain- As to compounds having a tertiary amine radical, it is obvious that one can employ derivatives of polyamines in which the terminal groups are unsymmetrically alkylated. Initial'polyamines of this type are illustrated by the following formula in which R represents a small alkyl radical such as methyl, ethyl, propyl, etc., and n represents a small whole number greater than unity such as 2, 3 or 4. Substituted imidazolines can only be formed from that part of the polyamine which has a primary amino group present. There is no objection to the presence of a tertiary'amine radical as previously pointed out. Such derivatives, provided there is more than one secondaryamino radical present in the ring compound, maybe reacted with an alkylene oxide, such as ethylene oxide, propylene oxide, glycide, etc., so as to convert one or more amino nitrogen radicals into the corresponding hydroxy alkyl radical, provided, however, that there is still a residual secondary amine group. For instance, in the preceding formula if n represents 4 it means the ring compound would have two secondary nitrogen radicals and could be treated with a single mole of an alkylene oxide and still provide a satisfactory reactant for the herein described condensation reaction.

Ring compounds, such as substituted imidazolines, may

be reacted with a substantial amount of alkylene oxide as noted in the preceding paragraph and then a secondary amino group introduced by two steps; first, reaction with an ethylene imine, and second, reaction with another mole of the oxide, or with an alkylating agent such as dimethyl sulfate, benzyl chloride, a low molal ester of a sulfonic acid, an alkyl bromide, etc.

As to oxyalkylated imidazolines and a variety of suitable high molecular weight carboxy acids which may be the source of a substituent radical, see U. S. Patent No. 2,468,180, dated April 26,1949, to De Groote and Keiser. Other suitable means may :be employed to eliminate a terminal primary amino radical. If there is additionally a basic secondary amino radical present then the primary amino radical can be subjected to acylation notwithstanding the fact that the surviving amino group has no sig-. nificant basicity. As a rule acylation takes place at the terminal primary amino group rather than at the secondary amino group, thus one can employ a compound such as '/NCH2 C11Hu cmtNmomtNn, 2-heptadecyl,1-diethylenediaminoimidazoline and.suhjectit to acylation so as to obtain, for example, acetylatedZ-heptadecyl,1-diethylenediaminoimidazoline of the following. structure:

N-CHr CnHarC (I) (15) N-CHQ -CHa C2H4.NH.C2H4.N

tive of 2-heptadecyl,l-arninoethylimidazoline, which can be. illustrated by the following formula:

Other, reactants. may be employed in connection with an initial reactant of the kind described above, to. wit, 2- heptadecyl,l-aminoethylimidazoline; for instance, reaction with an alkylene imine, such as. ethylene imine, pro.- pylene imine, etc. if reacted with ethylene imine the net. result. is; to; convert, a: primary amino, radical into a secondary amino radical and also introduces a new primary amino group. If ethylene imine is employed, the net result is; simply to convert 2:-heptadecyl,1-aminoethylimidazoline into Z-heptadecyl,l-diethylenediaminoimidazol-ine. However, if propylene imine is used the net result. is. a. compound which can be considered as being derived hypothetically from a mixed polyalkylene amine, i. e., onev having, both. ethylene groups and a propylene group between nitrogen atoms.

A moresatisfactory reactant is to employ one obtained by the reaction of epichlorohydrin on a secondary alkyl amine, such as thefollowing compound:

If a mole of Z-heptadecyl,l-arninoethylimidazoline is reacted with a mole of the compound just described, to wit,

the resultant compound has a basic secondary amino group and a basic tertiary amino group. See U. S. Patent No. 2,520,093 dated August 22, 1950, to Gross.

For purpose of convenience, what has been said by direct reference is largely by way of illustration in which there is present a sizable hydrophobe group, for instance,

heptadecyl groups, pentadecyl groups, octyl groups, nonyl groups,,etc. etc. p 7

As has been pointed out, one can obtain all these comparable derivatives from low, molal acids, such as acetic, propionic, butyric, valeric, etc. Similarly, one can employ hydroxy acids such as. glycolic acids, lactic acid, etc. Over and above this, one may employ acids which introduce a very distinct hydrophobe eflect as, for example, acids prepared by the oxyethylation of a low molal alcohol, such as methyl, ethyl, propyl, or the like, to produce compounds of the formula in which R is a, low molal, group, such as methyl, ethyl or propyl, and n is a. whole. number varying from. one up to 15 or 20. Such compounds can be converted into the alkoxide and then reacted with an ester of chloroacetic, followed by saponification so as to yield compounds of the type R(OCH2CH2)'1LOCH2COOH in which n has its prior significance. Another procedure is to con vert the compound into a halide ether such as in R(OCH2CH2 nCi in which n has its prior significance, and then react such halide either with sodium cyanide so as to give the corresponding nitrile, R(OCH'2CH2)1LCN, which can be convert'ed into the corresponding acid, of the following composition R(OCH2CI'-I2-)nCOOH. Such acids can also be used to produce acyl derivatives of the kind previously described in which acetic acid is used as an acylating agent.

What has been said above is intended to emphasize the fact that the nitrogen compounds herein employed can vary from those which are strongly hydrophobe in character and have a minimum hydrophobe property, to those which are essentially hydrophile in character and have only a very minimum hydrophobe property.

Examples of decreased hydrophobe character are exemplified by Z-methylimidazoline, Z-propylimidazolirie, and 2 butylimidazoline, of the following structures:

N-CH;

ilia-. (1

PART 3 The products obtained by the herein described processes represent cQgeneri'c, mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difiicu'lt' to actually depict the final product of the cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated from a resin, or in the manufacture of a phenol-amine-aldehyde resin; Or else from a particularly selected resin and an amine and. formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heatreactive resin. Since the condensation products obtained are not heatconvertible and since manufacture is not restricted to a single phase system, and since temperatures up to 150 C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus, I have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a ,polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethylene glycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in an oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can be used but it is more difficult perhaps to add a solid material instead of the liquid solution and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no

problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation,

then, obviously, the alcohol should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

Another factor, as far as the selection of solvent goes, is whether or not the cogeneric mixture obtained at the end of the reaction is to be used as such or in the salt form. The cogeneric mixtures obtained are apt to be solids or thick viscous liquids in which there is some change from the initial resin itself, particularly if some of the initial solvent is apt to remain without complete removal. Even if one starts with a resin which is almost water-white in color, the products obtained are almost invariably a dark red in color or at least a red-amber, or some color which includes both an amber component and a reddish component. By and large, the melting point is apt to be lower and the products may be more sticky and more tacky than the original resin itself. Depending on the resin selected and on the amine selected the condensation product or reaction mass on a solvent-free basis may be hard, resinous and comparable to the resin itself.

The products obtained, depending on the reactants selected, may be water-insoluble or water-dispersible, or water-soluble, or close to being water-soluble, Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amount of any selected acid and removing any water present by refluxing with benzene or the like. In fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over 15 0 C. and employing vacuum, if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc., can be used.- The selection of solvent, such as benzene, xylene, or the like, depends primarily on cost, i. e., the use of the most economical solvent and also on three other factors, two of which have been previously mentioned; (a) is the solvent to remain in the reaction mass without removal? (/5) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylationI; and the third factor is this, (0) is an effort to be made to purify the reaction mass by the usual procedure as, for example, a water-wash to remove the water-soluble unreacted formaldehyde, if any, or a waterwash to remove any unreacted water-soluble cyclic amidine, if employed and present after reaction? Such procedures are well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, I have found xylene the most satisfactory solvent.

I have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary, although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours.- I have not found any case where it Was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, I am'not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent thatit helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refluxiug should be long enough to insure that the resin added, preferably in a powdered form, is completely soluble. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the cyclic amidine is added and stirred. Depending on the polyamine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a three-phase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out I prefer to use a solution and whether to. use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

On a large scale if there is any difliculty with formaldehyde loss control, one can use a more dilute form of formaldehyde, for instance, a 30% solution. The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difliculties are involved. I have found no, advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homoeueous, at 30 or 40 C. for 4 or 5 hours, or at the most, up to -24 hours, I- then complete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of cyclic amidine or formaldehyde. At a higher temperature I use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. I then permit the temperature to rise to somewhere about 100 C., and generally slightly above 100 C., and below 150 C., by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued untilthe reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as. the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes I have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the selected cyclic amidine and 2 moles of formaldehyde. In some instances I have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases I have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In othe cases I have used a slight excess of, nitrogen compound and, again, have. not foundany particular advantage in so doing. Whenever feasible I have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not the end-product showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content .after removal of unreacted polyamine, if any is present, is another index.

In light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration;

Example 1b The phenol-aldehyde resin is the. one that has been identified previously as Example 2a. It was obtained from a paratertiary butyl phenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a slight amber color.

882 grams of the resin identified as 2a, preceding, were powdered and mixed with a somewhat lesser amount of xylene, i. e., 600 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 35 C. and 612 grams of 2-oleylimidazoline, previously shown in a structural formula as ring compound (3), were added. The mixture was stirred vigorously and formaldehyde added slowly. In this particular case the formaldehyde used was a 37% solution and 162 grams were added in approximately 3 hours. The mixture was stirred vigorously and kept within a range of approximately 40 to 44 C., for about 16% hours. At the end of this time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of unreacted formaldehyde was noted. Any unreacted formaldehyde seemed to disappear in approximately three hours after refluxing started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all the water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached approximately 148 C. The mass was kept at this higher temperature for 3 or 4 hours. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene. The residual material was dark red in color and had the consistency of a thick sticky fluid or tacky resin. The overall reaction time was approximately 30 hours. In other examples it varied from as little as 24 hours up to approximately 38 hours. The time can be reduced by cutting the low temperature period to approximately 3 to 6 hours. Note that in Table II following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of to 150 C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table II.

TABLE II Resin Amt Amt. of Strength of solvent used and Reaction Reaction Ex. No. used 3 Amine used amine, formaldehyde amt temp., time temp gr grams soln. and amt. 0. (hrs.) a O 2a Xylene, 600 g 30-25 30 148 5a Xylene, 450 g 21-23 24 145 a Xylene, 600 g 20-22 28 150 2a Xylene, 400 g 22-24 28 148 5a Xylene, 450 g 21-23 30 148 10a Xylene, 600 g 21-25 26 146 20 Xylene, 400 g 23-28 26 147 5a Xylene, 450 g 22-26 v 26 146 10a 21-25 38 150 13a 20-24 36 149 1401 21-22 142 15a -21 26 145 20 22-28 28 146 50 23-30 27 150 9a 20-24 29 147 2a 20-21 30 148 5a --do. 21-26 32 146 14a d0.. 21-23 26 147 22a 498 Amine 18. Xylene, 500 g 21-32 29 150 23a d Xylene, 500 g 21-30 32 150 25a Xylene, 550 g 21-23 37 150 24: Xylene, 440 g.. 20-22 1 26a Xylene, 600 g 20-25 36 149 27a 126 30%, 50 g Xylene, 400 g 20-24 32 152 The amine numbers referred to are the ring compounds identified previously by number in Part2.

PART FOUR In preparing oxyalkylated derivatives of products of the kind which appear as examples in Part 3, the procedures employed are substantially the same as those conventionally used in carrying out oxalkylations, and for this reason the oxyalkylation step will be simply illustrated by the following specific examples:

Example 1c The oxyalkylation-susceptible compound employed is the one previously described and designated as Example 1b. Condensate 1b was in turn obtained from 2-oleylimidazoline and the resin previously identified as Example 211. Reference to Table I shows that this particular resin is obtained from paratertiarybutylphenol and formaldehyde. 15.18 pounds of this resin condensate were dissolved in 6 pounds of solvent (xylene) along with 1.0 pound of finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave to operate at a temperature of approximately 125 C. to 135 C., and at a pressure of about 20 to 25 pounds.

In some subsequent examples pressures up to 35 pounds were employed.

The time regulator was set so as to inject the ethylene oxide in approximately three-quarters of an hour and then continue stirring for 15 minutes or longer, a total time of one hour. The reaction went readily, and, as a matter of fact, the oxide was taken up almost immediately. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to Wit, 15.18 pounds. This represented a molal ratio of 34.5 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was 3036. A comparatively small sample, lessthan 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data, or subsequent data, or in the data presented in tubular form in subsequent Tables 3 and 4.

The size of the autoclave employed was 25 gallons. In innumerable comparable oxalkylations I have withdrawn a substantial portion at the end of each step and continued oxalkylation on a partial residual sample.

This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a dilferent oxide.

Example 2c 30 This example simply illustrates the further oxyalkylation of Example 10, preceding. As previously stated, 1 the oxyalkylation-susceptible compound, to wit, Example lb, present at the beginning of the stage was obviously the same as at the end of the prior stage (Example 35 1c), to wit, 15.18 pounds. The amount of oxide present 'in the initial step was 15.18 pounds, the amount of catalyst remained the same, to wit 1.0 pound, and the amount of solvent remained the same. The amount of oxide added was another 15.18 pounds, all addition of 40 oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxycthylation step the amount of oxide added was a total of 30.36 pounds and the molal ratio of ethylene oxide to resin condensate was 69.0 to 1.0. The theoretical molecular weight was 3348.

The maximum temperature during the operation was 125 C. to 130 C. The maximum pressure was in the range of 20 to 25 pounds. The time period was one and one-half hours.

Example 30 Example 40 The oxyethylation was continued and the amount of oxide added again was 15.18 pounds. There was no added catalyst and no added solvent. The theoretical molecular weight at the end of the reaction period was 6072. The molal ratio of oxide to condensate was 138.0

to 1. Conditions as far as temperature and pressure were concerned were the same as in previous examples.

s The time period was slightly longer, to wit, 3% hours.

The reaction unquestionably began to slow up somewhat.

Example 50 The oxyethylation continued with the introduction of another 15.18-pounds of ethylene oxide. No more sol- 25 vent was introduced but .3 pound caustic soda. was added. The theoretical molecular weight at the end of the. agitation' period was 9108, and the molal ratio of oxide to resin condensate was 172.5 to l. The time period, however, dropped to 3 hours. Operating temperature and pressure remained the same as in the previous example.

Example 60 The same procedure was followed as in the previous examples. The amount of oxide added was another 15.18 pounds, bringing the total oxide introduced to 91.08 pounds. The temperature and pressure during this period were the same as before. There was no added solvent. The time period was 3 /2 hours. Molal ratio of oxide to resin condensate was 207.0 to one.

Example 7 c The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide. introduced at the end of the period was 106.26 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 12,144. The time required for the oxyethylation was a bit longer than in the previous step, to wit, 4 hours.

Example 80 This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 121.44 pounds. The theoretical molecular weight was 13,662. The molal ratio of oxide to resin condensate was 276.0 to one. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was 4 hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensates, described previously. All these data have been presented in tabular form in a series of 'four tables, Tables III and IV, V and VI.

In substantially every case a. 25-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a 15-gallon autoclave and then transferred to a ZS-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables III and IV, it will be noted that compounds 10 through 400 were obtained by the use of ethylene oxide, whereas 416 through 800 were obtained by the use of propylene oxide alone.

Thus, in reference to Table III it is to be noted as follows:

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to wit, the resin condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that ethylene oxide alone is employed, as happens to be the case in Examples 1c through 400, the amount of oxide present in the oxyalkylation derivative is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

The 8th column can be ignored where. a. single oxide.

was employed.

The 9th column shows the: theoretical molecular weight at the end of the oxyalkyla-tion period.

The 10th, column states the amount of condensate present in the reaction mass at they end of: the period.

As pointed out previously, in this. particular series. the amount of reaction mass. withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 10 coincides with the figure in column 3.

Column 11 shows the amount of ethylene oxide. employed in the reaction mass at the end of the particular period.

Column 12 can be ignored insofar that no propylene oxide was employed.

Column 13 shows the catalyst at the end of the reaction period.

Column 14 shows the amount of solvent at the end, of the reaction period.

Column 15 shows the molal ratio of ethylene oxide to condensate.

Column 16 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table. VI. It is to be noted that the first column refers to Examples 1c, 20, 30, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with several volumes of water, xylene and kerosene. It sometimes happens that although xylene in comparatively small amounts will dissolve in the concentrated material, when the concentrated material in turn is diluted with xylene separation takes place.

Referring to Table IV, Examples 410 through 800 are the counterparts of Examples 10 through 40c, except that the oxide employed is propylene oxide instead of ethylene oxide. Therefore, as explained previously, four columns are blank, to wit, columns 4, 8, l1 and 15.

Reference is now made to Table V. It is to be noted these compounds are designated by (1 numbers, 1d, 2d, 3d, etc., through and including 32d. They are derived, in turn, from compounds in the c seires, for example, 360, 40c, 54c, and 760. These compounds involve the use of both ethylene oxide and propylene oxide. Since compounds 10 through 400 were obtained by the use of ethylene oxide, it is obvious that those obtained from 360 and 400, involve the use of ethylene oxide first, and propylene oxide afterward. inversely, those compounds obtained from 540 and 76c obviously come from a prior series in which propylene oxide was used first.

In the preparation of this series indicated by the small letter a', as 1d, 2d, 3d, etc, the initial 0 series such as 360, 40c, 54c, and 760, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may have been the case in the original oxyalkylation step. Then oxyalkylation proceeded by using the second oxide as indicated by the previous explanation, to wit, propylene oxide in 1d through 16d, and ethylene oxide in 17d through 32d, inclusive.

In examining the table beginning with 1d, it will be noted that the initial product, i. e., 36c, consisted of the reaction product involving 15.18 pounds of the resin condensate, 22.27 pounds of ethylene oxide, 1.0 pound of caustic soda, and 6.0 pounds of the solvent.

It is to be noted that reference to the catalyst in Table V refers to the total amount of catalyst, i. e., the catalyst present from the first oxyalkylation step plus added catalyst, if any. The same is true in regard to the solvent. Reference to the solvent refers to the total Solvent present,

' 27 i. e., that from the first oxyalkylation step plus added solvent, if any.

In this series, it will be noted that the theoretical molecular weights are given prior to the oxyalkylation step The colors of the products usually vary from a reddish amber tint to a definitely red, and amber. The reason is primarily that no efiort is made to obtain colorless resins initially and the resins themselves may be and after the oxyalkylation step, although the value at .3 yellow, amber, or even dark amber. Condensation of the end of one step is the value at the beginning of the a nitrogenous product invariably yields a darker prodnext step, except obviously at the very start the value uct than the original resin and usually has a reddish depends on the theoretical molecular weight at the end color. The solvent employed, if xylene, adds nothing of the initial oxyalkylation step; i. e., oxyethylation for to the color but one may use a darker colored aromatic ld through 16d, and oxypropylation for 17d through 32d. petroleum solvent. Oxyalkylation generally tends to It will be noted also that under the molal ratio the yield lighter colored products and the more oxide emvalues of both oxides to the resin condensate are included. ployed the lighter the color of the product. Products The data given in regard to the operating conditions is can be prepared in which the final color is a lighter substantially the same as before and appears in Table VI. amber with a reddish tint. Such products can be decol- The products resulting from these procedures may conorized by the use of clays, bleaching chars, etc. As far tain modest amounts, or have small amounts, of the sOlas use in demulsification is concerned, 01- some other Vents as indicated y figures 1n the tables- If desired industrial uses, there is no justification for the cost of the solvent may be removed by distillation, and particubleaching the product larly vacuum distillation. Such distillation also may If the oxyalkylated derivatives were not used in sub remove traces of F amounts of Pilcombmed oxlde, 1f 20 sequent esterification reactions, then alkalinity, whether z l i unde; i li g g g De due to an amino nitrogen atom or added catalyst, would i b use 0 e yene 0X1 6 n Pr.pye be immaterial for many purposes. For esterification oxide in combination one need not first use one oxide and it is preferable that the alkalinity be eliminated in an then the other, but one can mix the two oxides and thus one of a number of Wa add an a id l obtain what may be termed an inditferent oxyalkylation, t h I d d t 1 t g rt th l iqi 611 i. e., no attempt to selectively add one and then the other, 9 e a ca a ys 8 ca a ys mm or any other variant. dium chloride and the amine radical into a hydrochlo- Needless to say, one could start with ethylene oxide and Tlde; or (C) use an excess of PolycarbQXy feactalit then use propylene oxide, and then go back to ethylene Y though 3 E Percentage is wasted- All thls 1S id i l start ith propylene id th discussed in detail in the next section. More careful use ethylene oxide, and then go back to propylene oxide; examination of this type of material can be made by or, one could use a combination in which butylene oxide methods employing the well known Karl Fischer reis used along with either one of the two oxides just menagents as described in Aquametry, Smith and Mitchell, tioned, or a combination of both of them. Jr., lnterscience Publishers, New York, 1948.

TABLE III Composition before Composition at end Mela-l ratio Ex. No. 0-8 I 1 0-8 Ethyl. Propl. Cata- Sol- Theo. lheo. O-S" Lthyl Propl. Cata- S01- gz cmpd., oxide, oxide, lyst, vent, n10]. mol. cmpd., oxide, oxide, lyst, vent, 358g:

lbs. lbs. lbs. lbs. lbs. wt. Wt. lbs. lbs. lbs. lbs. lbs. to resin to resin condencondensate sate 'Oxyalkylation-susceptlble.

TABLE IV Composition before Composition at end Molal ratio Ex No. -5

' O-S Ethyl. Prop]. Oata- Sol- Theo. Theo. O-S' Ethyl. Prop]. Oata- Solgif cmgld oxide, oxide, lyst, vent, mol. mo]. cmpd., oxide, oxide, lyst, vent, 338;

No 1 s. lbs. lbs. lbs. lbs. wt. wt. lbs. lbs. lbs. lbs. lbs. to resin to resin condencondensate sate 15. 1.1 6.0 3, 036 15. 18 15.18 1. 1 6.0 26. 2 1.1 6.0 4, 554 15.18 30.36 1. 1 6.0 52. 4 15. 1. 1 6.0 6, 072 15.18 45.54 1. 1 6.0 78. 6 1.1 6.0 15.18 60.72 1. 1 6. 6 104.8 1.1 6.0 15.18 75.90 1.1 6.0 131.0 1. 5 6.0 15.18 106.26 1. 5 6.0 183.4 15. 1. 5 6. 0 15. 18 136. 62 1. 5 6.0 235. 8 1. 5 6. 0 15. 18 166.98 1. 5 6.0 288. 2 1. 1 4. 5 15. 46 15. 46 1. 1 4. 5 26. 6 1. 1 4. 5 15.46 36. 92 1. 1 4. 5 53. 2 1. 1 4. 5 15.46 46. 38 1. 1 4. 5 79. 8 1.1 4. 5 15. 46 61.84 1.1 4. 5 106.4 1. 1 4. 5 15. 46 77. 30 1. 1 4. 5 133. 0 1. 5 4. 5 15. 46 108. 22 1. 5 4. 5 186. 2 v 15. 1. 5 4. 5 15.46 139. 14 1. 5 4. 5 239. 4 1. 5 4. 5 15. 46 170.06 1. 5 4. 5 292. 6 1. 2 4. 5 17. 74 17. 74 1. 2 4. 5 30.6 1.2 4.5 17. 74 35.48 1. 2 4. 5 61.2 1. 2 4. 5 17. 74 53. 22 1. 2 4. 5 91. 8 1. 2 4. 5 17.74 70. 96 1.2 4. 5 122. 4 17. 1. 2 4. 5 17. 74 88. 70 1. 2 4. 5 153.0 88.70 1. 7 4. 5 17. 74 124. 18 1. 7 4. 5 214. 2 124. IS 1. 7 4. 5 17. 74 159. 66 1. 7 4. 5 275. 4 159. 66 1. 7 4. 5 17. 74 195. 14 1.7 4. 5 336. 6 11.58 1.0 4. 4 11.58 11.58 1.0 4. 4 19. 95 11. 58 11.58 1.0 4. 4 11.58 23.16 1.0 4. 4 39. 90 11.58 23.16 1. 0 4. 4 11. 58 34. 74 4. 4 59. 80 11. 58 34. 74 1. 0 4. 4 11.58 46. 32 1.0 4. 4 79. 80 11.58 46. 32 1.6 4. 4 11.58 57. 96 1.0 4. 4 99. 60 11.58 57. 90 1.5 4. 4 11.58 81.06 1. 5 4. 4 140.6 11.58 81. 06 1. 5 4. 4 11.58 104. 22 1. 5 4. 4 180.0 11. 58 104. 22 1. 5 4. 4 11.58 127. 38 1. 5 4. 4 219. 9 15. 18 1.0 6.0 15.18 7. 59 1. 6 6.0 13.15 15. 18 7. 59 1.0 6. 0 15. 18 15.18 1.0 6.0 26. 3 15.18 15. 18 1. 0 6.0 15. 18 22. 77 1.0 6.0 39. 45 15.18 22. 77 1.0 6.6 15.18 30.36 1. 0 6.0 52. 60 15.18 30. 36 1. 6 6.0 15. 18 37. 95 1.0 6.0 65. 75 15.18 37. 95 1.4 6.0 15.18 53.13 1. 4 6.6 92. 05 15.18 53. 13 1. 4 6.0 15. 18 68. 31 1. 4 6.0 118. 35 15. 18 68. 31 1. 4 6. 0 15. 18 83. 49 1. 4 6.6 144.65

*Oxyalkylatlon-susceptible.

TABLE V Composition before Composition at end Molal ratio Ex. N0. O-S

O-S Ethyl. Pmpl. Cata- Sol- Theo. Theo. 0-S Ethyl. Prop]. Cata- Solg cmpd., oxide, oxide, lyst, vent, 11101. 11101. cmpd., oxide, oxide, lyst, vent, Egg;

No lbs. lbs. lbs. lbs. lbs. wt. wt. lbs. lbs. lbs. lbs. lbs. to resin to resin condencondensate sate 15. 18 30. 36 1.0 6. 0 4, 554 5, 313 15.18 36. 36 7. 59 1.6 6.0 68.8 13. 15. 18 30. 7. 59 1.0 6. 0 313 6, 672 15. 18 30 36 15. 18 1.0 6. 6 68.8 26. 15 15. 18 30. 36 15. 18 1. 0 6.0 6, 072 6, 831 15. 18 30. 36 22.77 1.0 6. 0 68. 8 39. 15. 18 30. 36 22. 77 1-0 6.6 6,831 7, 590 15. 18 30.36 30. 36 1.0 6.0 68. 8 52. 3 15. 18 30. 36 30. 36 1. 0 6.6 7, 590 8, 349 15. 18 36. 36 37.95 1.0 6. 0 68. 8 60. 5 15.18 36. 36 37. 95 1.0 6. 0 8,349 9, 108 15.18 30.36 45. 5 1. 5 6.0 68.8 78. 6 15. 18 30. 36 45. 54 1. 5 6.0 9, 108 10, 626 15.18 30.3 60. 72 1. 5 6.6 68.8 104. 8 15 30. 36 66. 72 1. 5 6. 6 10, 626 12, 144 15. 18 30. 75. 96 1. 5 6.6 68.8 131.8 15 18 60. 72 1. 3 6.0 7, 590 8, 349 15. 18 60.72 7. 1. 3 6.6 137. 6 13.1 15. 18 60. 72 7. 59 1. 3 6. 0 8, 349 9, 108 15. 18 60. 72 15. 18 1.3 6. 0 137. 6 26. 2 15.18 66. 2 15. 18 1. 3 6.0 9 108 10, 626 15. 18 60.72 30.36 1. 3 6.6 137. 6 52.4 15. 18 60.72 30. 36 1. 3 6.0 16, 626 12, 144 15. 18 60. 72 45. 54 1. 3 6. 6 137. 6 78. 6 15. 18 60. 72 45. 54 1. 3 6. 0 12, 144 13, 662 15.18 60. 72 60. 72 l. 8 6.0 137. 6 164. 8 15.18 60. 72 60. 72 1. 8 6. 0 13, 662 14, 421 15.18 60.7 68.21 1. 8 6.0 137. 6 117. 9 15. 18 60.72 68.21 1. 8 6.0 14, 421 15, 180 15.18 60.72 75.90 1. 8 6.0 137. 6 131.0 15. 18 60. 72 75.90 1. 8 6. 0 15, 186 16 698 15. 18 60.72 91. 08 1. 8 6. 0 137. 6 157. 2 15. 46 108. 22 1. 5 4. 5 13, 914 14, 300 15 46 3. 86 108. 22 1. 5 4. 5 8. 75 186. 2 15.46 3. 86 108.22 1. 5 4. 5 14,300 14, 687 15 46 7. 73 108. 22 1. 5 4. 5 17.6 186. 2 15. 46 7. 73 108. 22 1. 5 4. 5 14,687 15, 460 15 46 15.46 108. 22 1. 5 4. 5 35. 2 186. 2 15.46 15.46 108. 22 1. 5 4. 5 4 16, 333 15. 46 23. 19 168. 22 1. 5 4. 5 52. 8 186. 2 15.46 23. 19 108. 22 1. 5 4. 5 16, 333 17, 106 15 46 30. 92 168. 22 1. 5 4. 5 70.3 186. 2 15. 46 30. 92 108. 22 1. 5 4. 5 17, 106 16, 879 15 46 38. 65 108. 22 1. 5 4. 5 87. 9 186. 2 15.46 38. 65 108. 22 1. 5 4. 5 17, 879 18, 6 15 46 46.38 108. 22 l. 5 4. 5 105. 2 186. 2 15.46 46. 38 108. 22 1. 5 4. 5 18, 652 19, 425 15. 46 54. 11 108. 22 1. 5 4. 5 123.0 186. 2 15. 18 30. 1. 6 6.0 4, 554 5, 313 15 18 7. 59 30. 36 1. 0 6. O 17. 52.6 15. 18 7. 59 30. 36 1. 0 6.0 5, 313 6, 072 15 18 15.18 30.36 1.0 6.6 34. 50 52.6 15. 18 15. 18 30.36 1. 0 6.0 6, 072 6,831 15. 18 22.77 36. 1.0 6.0 51. 52. 6 15. 18 22. 77 30. 36 1. 0 6. O 6, 31 7, 590 15. 18 30.36 30.36 1.0 6. 0 69.0 52. 6 15.18 30.36 30.36 1.0 6. 0 7 590 9,108 45.54 30. 36 1. 5 6.0 103.0 52.6 15. 18 45. 54 36.36 1. 5 6.0 10 10, 626 15 18 60. 72 30. 36 1. 5 6.0 138. 2 52. 6 15. 18 60. 72 30. 36 1. 5 6.6 10, 626 12, 144 15. 18 75.96 30. 36 1. 5 6. 0 172. 2 52. 6 76. 15. 18 75. 36. 36 1.5 6.6 12, 144 13, 662 15. 18 91.08 30.36 1. 5 6. 0 207.0 52. 6

Oxyalkylation-susceptlble.

TABLE VI TABLE VI-Continued Ex. Time, Solubihty Ex Max. Max. Time 7 Solubility i g. Pres, hrs. temp pres, hrs

' Water Xylene Kerosene p.s.1. water xylene Kerosene 1c 125-135 20-25 1 25d. 130-135 15-20 V Insoluble 3015315.. Insoluble. 2a.. -135 0-25 2511. 130-135 15-20 1 21511151115515... .do Do. 35.. 125-135 20-25 3 275. 130-135 15-20 2 ..do -410... Do. 45.. 125-135 20-25 284. 130-135 15-20 do. Do. 55.. 12 -135 20-25 3 10 205.130-135 -20 -do Do. 05.. 125-135 -25 3 300. 130-135 15-20 Insoluble Do.

33 :1 31- 133 3 C a 9L 1 53 2 35 5-20 do D0. 100. 5- 5 0 3:-

33 15 PART 5 a @133 1: As previously pointed out, the present invention is con- 51; 15 -21 cerned w1th acidic esters obtained from the oxyalkylated 9i- 125 135 1045 1:21;: derivatives described in Part 4, immediately preceding, 13,; 125-135 10-15 1% and 01 carbox ac'ds g 125-135 10.15 2% s bl y l pairucularly (heal-boxy i su.ch 206 125435 1H5 3 d 20 as ad1p1c ac1d, phthahc acid, or anhydrlde, succm1c ac1d, gc. 1&1? dlglycolic acid, sebacic acid, azelaic acid, aconitic acid, 2 125435 1045 maleic acid or anhydricle, citraconic acid or anhydride, 24c 125-135 10-15 malelc acid or anhydride adducts, as obtained by the 250. 130-135 30-35 v 26L EH35 30455 Dlels-Alder reaction from products such as male1c an- 273 130-135 30-35 hydride, and cyclopentadiene. Such acids should be 233, 130-135 30-35 29L 130435 30.35 heat-stable so they are not decomposed durlng estenfica- 305 130-135 30-35 tion. They may contain as many as 36 carbon atoms as, 31 130-135 30-35 320 130.135 3H5 for example, the ac1ds obtalned by d1mer1zat1on of unggg. 3&2? saturated fatty ac1ds, unsaturated monocarboxy fatty 130.135 30.35 30 acids, or unsaturated monocarboxy acids having 18 cargi 38:32 bon atoms. Reference to the acid in the hereto ap- 3 :130 135 3H5 pended clalms obv ously includes the anhydrides or any 232: other obvlous equivalents. My preference, however, is 415.125-130 25-35 2 Insoluble. to use polycarboxy ac1ds, and part1cularly dicarboxy figgfjgg 52:22 Dispegime 35 acids,'having not over'8 carbon atoms. 445 125-130 25-35 4 Soluble. In the present instance the polyhydroxylated reactants :22-

IM B3: have at least two or more hydroxyl radicals. Indeed, 47 125-130 25-35 5% Do. assuming the resin unit has three or more phenolic by- 132 fifigg 33:2? 3 I ns {5 droxyls which always would be true, oxyalkylation neces- 50 135-140 30-35 2% Do. sarily must yield at least three reactive h drox 1 radicals 1 3 D1 bl 0 y 2; 2 323 2&2? 4% Z S except 1n the very early stages or very low l11n1t of ox- 35 135-140 30-35 5 Do. yalkylation as described in the preceding section. If 2%; {gigs 28:22 2 zf glycide or methylglycide were used the number of hy- 56c 135-140 30-35 0% Do. droxyl radicals would be larger. Since the phenolic 2g: 3 5f; resin itself may have several phenolic hydroxyls there is 59c 125-135 30-35 3 Do. further opportunity for a multiplicity of hydroxyl radicals 2 3&2? 21 in the reactant which serves as an alcohol in the esterifi- 620 125-135 30-35 4 Do. cation step. The presence of a basic nitrogen atom in- 822 5g: 2 8g: volves some added complication due to its inherent salt- 65c 0-135 30-40 Insoluble. forrnin character. If several basic nitro en atoms ha 66c 130-135 30-40 Do p 67c 13o 135 3040 mspersibm pened to be present 111 a polyhydroxylated reactant the 33- 130-135 30-40 solu lglesame would be'true to a greater degree. In any con- 93f,- figg 818 4 31 densate of the general type herein described, *and also 710 30-135 30-40 41 5. in the type of condensate described in my co-pendin 720 30-135 30- 40 6 Do g 73L 130435 W20 2 1 5 apphcations, Serial Nos. 321,031, 321,032, 321,033, and 7 4 E 20 80- 321,034, invariably there must be at least two baSlC 760. 130-132 15-38 DgI nitrogen atoms. 770. 130-135 15-20 Dl pe It is my reference alwa s to add enough of a strong 7811 30-135 15-20 Soluble 1 p 130435 1H0 acid, such as hydrochloric acid or sulfunc acid, so as to if 352 I 9 be st01ch1ometr1cally equivalent to the basicity of the 241130435 304,5 j alkaline catalyst used in oxyalkylation. Also, I prefer i5 2&3; g to use a slight additional excess and if need be suflicient' 3113 30 35 j mspefigibla to combine with the nitrogen basicity of the reactant,

Solubleand 1f needed an excess over and above the amount. 8d: 130-135 30-35 At the worst, if there is no excess, some of the poly- 131.. 130-135 30-35 carboxy acid reactant may be wasted in a neutralizing 1011.130-135 30-35 11d -135 30-35 reactlon rather than an estenfication reaction. Such salt {55 may, however, convert into an ester. However, it is 1%.120-135 t io-35 my preference to use the oxyalkylated derivatives in 16d: 133322 me 70 which the original resin condensate contributesa com- ;gg D paratively small fraction and thus the bas1c1ty may in 190'. -140 30-35 I itself either be insignificant jor comparatively small from 3%: 1323:? 1 a neutralization standpoint. With these facts in mind 224. 135-140 30-35 2% Do. one can prepare the esters in substantially the same way 234. 135-140 30-35 3 Insoluble. 244. 135-140 30-35 3% Do. 76

as if one were esterifying polyhydroxylated reactants free 'cation temperature is too high.

, rate so as to keep the reaction mass acidic.

- basiematerial.

any nitrogen atom, particularly .any basic nitrogen :a'tom.

Asstated in U.. SfPaltent No. 2,602,060 dated July v1, IS'SZLto'DeGrbote, 'the'production of esters, including (acidic *esters (fractional esters) from polyearboxy acids glycolsor other hydroxyla'ted compounds, is well known. N eedless 'to say, various compounds may;be used, such as the.low molal ester, the anhydride, the a'cyl'ehloride, .etc. However, .for purpose of economy it is customary to use either the acid or'the anhydride. A conventional procedure is employed. On a laboratory scale one can employ a'resin pot of the kind described in U. S. Patent No."2,499,370, dated March 7, 1950, to 'De'Groote "and Keiser, and particularly'with one more opening to 'PCllIllhthfi use of a porous spreader if hydrochloric acid gas is 'to'be used as.a catalyst. Such device or absorption spreader consists of minute Alundum "thiiribles which are connected to a glasstube. One can add a sulfonic acid such as paratoluene sulfonic acid as a catalyst. There is some objection to this because in some instances there is some evidence that this acid catalyst tends to decompose or rearrange polyoxyalkylated compounds,'and particularly likely to do so if-the esterifi- In the case .of poly- 'carboxy acids such as diglycolic which is strongly acidic, "th'ereis no need to add any catalyst.

'Infthe case of highly oxyalkylated compounds. where nitrogen .basicity can beignored, or almost ignored, the use of hydrochloric gas .has one advantage over paratoluene sulfonic acid and that is that at the end of the reaction it can be removed by flushing out with nitrogen,

whereas there is no reasonably convenient means available of removing the paratoluene sulfonic acid or other sulfonic acid employed. If hydrochloric acid is employed one need only pass the gas through at an exceedingly slow Onlya trace of acid need be present. I have employed hydrochloric acidgas or .the aqueous acid itself .to eliminate the initial My preference, however, is to use no catalyst whatsoever and to insure complete dryness of the oxyalkylated amine-modified phenol-aldehyde resin as described :int he final procedure just preceding Table VII.

The products obtained in lPart 4, preceding, may contain a basic catalyst. pounds, as a general procedure I have added an amount of half-concentrated hydrochloric acid considerably in excess of.what is required .to neutralize the residual catalyst. The mixture is shaken thoroughly and allowed to stand overnight. It is then filtered and refluxed with the xylenewpresent until the water can be. separated in a'phasei-separating trap. Assoon as the product is substantially free from water the distillation stops. This preliminary, step can be carried out in the flask to be usedfor esterification. If there is .any further deposition of sodiumchloride during the reflux stage, needless to say, a second filtration mayxbe required.

'In any event, the product resulting from the pretreatment is apt to be neutral or 'basic and particularly slight ly basic. If a little more acid is used it may'even'be acidic. My preference is, as pointedout previously, that the product be neutral or slightly acidic. Oddly enough, .alltheibasicity is-due to a basic nitrogenatom or more than one basic nitrogen .atomsincethe resin condensate :must invariably and inevitably have at least two basic 'nitrogen atoms, I have found that in'stagesof modest or :heavy oxyalkylation the final'produc't indicates that the basicity. has been greatly'reduced, possibly due 2to the hydroxylation or some other effect. ample, the. reduced basicity of triethanolamine with that 'of ammonia. As previouslynoted, at the -worseif all the catalyst has been removed or neutralized, alittle 0 the polycarboxyireactant maybe lost.

Considering the-resin condensates which are subjected to-oxyalkylation,inot only in the present applic'atiombutalso in the four co-pending applications, Serial'Nos.

Using highly oxyalkylated .com-' Compare, for ex-' 321,031, 321,032,- 3'21,033, and 321,034, it is apparent the situation becomes further complicated by the fact that an amine having one or more basic nitrogen atoms, or even a cyclic structure, also may have hydroxyl radicals and possibly secondary nitrogen groups susceptible, to acylation. 'Sueh-aniino groups are apt to disappear for obvious reasons on oxyalkylation, particularly after the initial step of oxyalkylation. Thus, what is said herein in regard to esterification applies with equalforce and efiect substantially to all hydroxylated compounds described, not only-in this application but also .in thefour co-pending applications noted immediately above.

In any event, such oxyalkylated derivativesdescr'ibedtin Part Four is then-diluted.further with sufiicient xylene, decalin, petroleum solvent, or the like, so that one has obtained approximatelya ,solution. Toy-this solution there is-added a-polycarboxylated reactant,-as .pre-

tion is complete .as indicated-by elimination of water or .drop in carboxyl .value. Needless to say, if one-produces a half-ester from ananhydride-such-as'phthalic anhydride, no water is eliminated. However, if 'it is obtained from diglycolic acid 'for example, water '"is eliminated. All suchv procedures are conventional and have beenso thoroughly described .in .the literature that further consideration will be limited 'toia few examples and a comprehensive table.

Other procedures for eliminating the basic residual catalyst, if any, can be employed. For example, the oxyalkylation can be conducted in absence of a solvent or the solvent removed after oxypropylation. Such oxyalkylated end-product can then be acidified with just enough concentrated hydrochloric acid to just neutralize the residual 'basic catalyst. To this product onecan then add asmall amount of anhydrous-sodium sulfate (sufiicient in quantity to take up anywater that is-present) and then subject the 'ma'ss to centrifugal force so as to eliminate the dehydrated sodium sulfate and probably the what has been said previously in regard to basicity due to the basic nitrogen atoms present.

It .isto be pointed out that the products here described are not polyesters in the' sense that 'there is a:plurality of both hydroxy reactant radicals and acid radicals; the product is characterized'by having only one'hydroxy reactant radical.

Insome instances and,in fact, in many instances, I have found that inlspite of'the dehydration methods employed above a mere-trace of water still comes -through,-.and that this mere trace of water certainlykinterferes with the acetyl or hydroxyl value .determination, at least when a number of conventional procedures are used and may retard esterification particularly where there is no sulfonic acid-or hydrochloric acid present as va catalyst.-- There- 'fore, I have prferredto use the following procedure: I have employed about 200 grainsof the hydroxylated compound as described in Part -F0ur,;preceding; I have added about 200 grams of benzene, and then refluxed this mixture in the glass :resinpot using a phase-separating'trap until the benzene carried out all the water present as water of solution-or the equivalent. Ordinarily 5 1111., 200 c; 1111., 244 c. -10 1111., 209 0. 1111., 248 0. 151111., 215 c. I '65 1111., 252 c. 20 1111., 216 c. 1111., 252 c. 251111., 220 c. 1 1111., 260 c. 301111., 225 0. 1111., 264 0. as 1111;, 250 0. I 1111., 270 c. 40 1111., 234C. 901111., 280 0.. 45 1111., 237 c. '95 1111., 30720.

' After this material is added, refluxing is continued and, 'of c0urse, is at a hightemperature, to wit, about 'to C. If the carboxyreactant is'an anhydride, needless to say, no water of reaction appears; it the carboxy reactant is anacid. watenof reaction shouldappear and should be eliminated -at the above reaction temperature. Ifv it is not eliminated, I simply separate outanother 5 to 10 cc. of benzene by means of the phase-separating trap and'thus raise the temperatureto'180or 190 C., or even to 200 C., if need be. My preference is not togoabove200C.-'

' The use of such solvent is extremely satisfactory, provided one' does not attempt to'remove the solvent subsequently except by vacuum distillation, and provided there is no objection. to a (little 1r sidue. Actually, when these materials are used for a purpose such as der'nulsific ation thesolvent might just. as well be allowed to remaini fi the solvent is to be removed 111 6186116061,1.11111 111111611- larly vacu'u'rn'distillation, then the. high'boiling aromatic petroleum solvent might well be replaced by some more expensive solvent such as decalin or 'an alkylated decalin,

1111160 1111 a rather definite or close range boiling point. The removal of solvent, of course, is purely aconventional procedure and requires no elaborationl l f' Merely by way of illustration, the following examples use a simple procedu're, to wit; the hydroxylated compound is rnixedwith an equal weight 'of xylene and refluxed at approximately 190 C., or thereabouts for 12 hours "or somewhat longer. After this'period oftime it has been found that in almost every instance .1116 reaction is complete. Water,'if formed, 1116115111 1 1 by the usual trap arrangement. Of course, when ianhydride is used thereis' little or no formation of water. 1

. Example 1a .was almost 16 hours. 'Theamount'of water out at the end of this period was 1.2 grams. The same procedure was followed in anumber of other examples, all of which 30 are included in'Table VII, following.

TABLE VII Amt. of 1 Max Amt. of Time of Theo. Hyd. Solvent estenfi- Ex. No. polycarb. estenfi- Water acid ester hgidfi v51. cllrgd. Pol: carboxy reactant reactant (xygssne), ggxtxign, cation, out cc. 7 grs. 11 hrs.

18. 2 200 Diglycolic acid 8. 81 207. 6 200 13.2 200 Phthalie anhydride. 9. 75 209.8- 204 7 18. 2 200 Maleic anhydrlde. 6. 45 206. 5 193 18. 2 200 Aconitir? ae1d. 11.5 v 210. 3 195 1.5. 9. 200 Diglyeolic ac1d 7. 71 206. 7 1 202 15. 9 200 Phtlmlic anhydr1de 8. 53 208. 5 201 15.9 200 Maleic anhydri e. 5. 65 205. 7 195 15. 9 200 Adipic ac1d 8. 4 207. 4 198 14. 1 200 Diglycolic aeld. 6.36 205.4 205 14. 1 200 Phthalle anhydnd 7. 59 1 207. 6 203 14. 1 200 Maleie anhydride. 5. 01 205. 0 200 14.1 200 Succim'c anhydride. 5.12 205. 1 198 1 16.8 200 s; 04 207. 4 p 203 16. 8 200 0. 55 209. 6 199 16.8 200 6. ,34 206. 3 1 195 16. 8 200 11.25 210. 1 197 15. 6 200 7. 58 206. 6 205 r 15.6 200 8.36 208.4 203 15.0 200 5.54 205. 5 198 15. 6 200 8.25 v208. 3 203 1 13. 9 200 p 6. 80 206. 0 209 13. 9 200 7. 6 207. 6 207 13. 9 200 4. 93 204. 9 109 13. 9 200 5. 13 205. 1 195 14. 1 200 6.85 200 14.1 v 200 7. 58 207 6 211 14. 1 200 Maleic anhydride 5. 02 205 202 14.1 V 200 Aeonitic acid"... 8:9 208 207 11.6 200 Diglycolie acid 5. 64 204.8. 210

11. 6 Phthalic .6. 22 206. 2. 214 11. 6 4. 12 204. 1 206 11.6 6.14 205.3 209 10.6 5.03 204.3 "215 10. 6 5. 55' p 205. 6 212 10.6 3. 75 203.8 202 10. 6 3. 83 203. 8 .205 13. 85 6. 75 205. 9 208 13.85 I 7. 45 207.5 207 '13. 85 4.94 204.9 199 13. 85 8. 75 207. 9 t 202 11. 3 5. 51. 204.8 202 11.3 6.1 206.1 199 11. 3 4. 03 204 v 188 11. 3 7. 16 206. 4 '193 10.4 5.05 204.35 200 10.4 5.58 205.6 108 10. 4 3. 70 203. 7 191 10. 4 3. 77 203. 8 21.2 10.3 209 185 21. 2 '11. 4 211. 4 188 21.2 7. 52 207.5 179 v21. 2 13. 4 212. 1' 183 18. 1 8. 84 207. 6 1.90 '18. 1 200 Phthalic anhydride. 9. 75 209. 8 189 18.1 V 200 Malelc anhydride- 6. 45. 206.5 179 18. 1 200 Adiplc acid I 9. 6 208.4 182 15.9 200 Diglycollc a'o1d.' 7. 7 206.7 192 15. 9 200 Phthalic anhydr1de-- 8 5 208. 5 190 Talents; VII-Continued Amt of Time of Theo hyd. Solvent esterifi- Ex. No. Ex. No. Theo.m w polycarb. on esterlfi Water acid ester of (mm of c hoytdfiivgl cllrgfi. Polycarboxy reactant reactant, (io glf u 2 2 hmn, out, cc

grs. TS.

12,144 .15. 9- 200 ,Malele anhydride 5. 65 205; 7 183 12, 144 15. 9 200 Succinic anhydride.. 5. 75 205. 8 184 10 17, 870 10:8 200 Diglycollcacidwu 5. 204. 6 197 15 7 17, 879 10. 8 200 hthallc anhydrld 5. 8 205. 8 195 17 17, 879 10. 8 200 Maleic snhydride" 3. 84 203. 8 188 12 17, 879 10; 8' v 200 Aconitic acid 6. 82 206. 1 192 13 18, 652 10c z .200- Dlglycolle acid. 5. 03 204. 3 202 15 18, 652 10. 35 200' Phthallc anhydrtde- 5. 55 205. 6 200 15 18, 852 10.-35 200 Maleicanhydrida. 3. 68 203. 7 192 10 18, .652 10. 35 200 :Adlpic acid 5. 47 204. 8 195 12 425 9. 94 200 7 'Diglycolioacld 4. 83 204. 2 205 15 19, 425 0. 94. 200 'Phthalicanhydride 5. 33 205. 3 202 16 19, 425 9. 94 200 Maleic anhydride. 3. 52 203. 5 195 13 19, 425 9. 94 200 Succinlc anhydride 3. 6 203. 6 194 8 PART 6 some other chemical demulslfier. A mixture whrch illus- Conventional demulsifying agents .ernployedin the treatmentof oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene,;tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol,: ethylv alcohoL' denatured alcohol, propyl alcohol, butylalcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents. such as pine .oil, carbon tetrachloride, sulfur dioxide extract obtained .in the refining of petroleum, etc., may be employed :as diluents. Similarly, the material or materials employed as:.the demulsifying agent of my process may be admixed with one or more of the solvents customarily used in connection'with. conventional demulsifying agents. Moreover, said material or materials may be used alone or :in admixture with other suitable well-known ,classesuof demulsifying' agents. It is well known that conventional 'demulsifyinglagents may be used in a water-solublefonm-ortin anion-soluble form, or in a form exhibiting both oil-..and water-solubility. Sometimes they may be usedmin :aiiornr which exhibits relatively limited 'oilsolubilityQ However;.-since such reagents are frequently used .inaira'tio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1' to 40,000, or 1 to 50,000 as in desalting. practice, such an apparent-insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such'concentrations. This same fact is true in regard-to the'material or materials employed as the demul'sifying agent of my process.

In practicing the present process the treating or demulsifying agent is employed in 'the conventionalmanner, well known to the art, described for example in-"Patent 2,626,929, dated January 27, 1953, Part '3, and reference is made thereto for a description of conventional 'pro- A cedures of demulsifying, including batch, continuous and down-the-hole demulsification, the process essentiallyinvolving introducing a small amount of demulsifier-i'nto a large amount of emulsion with adequate admixture, with or without the application of heat, and allowing the mixture to stratify.

In many instances the oxyalkylated products herein specified as demulsifiers can be conveniently used without dilution. However, they "may be diluted as desired with any suitable solvent. parts by Weight of an oxyalkylated derivative, for example, the product of Example 612 with 115 parts by weight of xylene and 10 parts by weight of 'isoprqpyl alcohol, an excellent demulsifier is obtained;- .Selection of the solvent will vary, depending upon the solubility characteristics of the oxyalkylated product, and of course :will be dictated in part by economic considerations, i. e., cost.

The'products herein described may be used not only in diluted form, but also may be used admixed with trates such combination is the following:

Oxyalkylated derivative, for example, the product of Example 6le, 2.0%; p i 1 A cyclohexylamine salt of a polypropylated napthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated napthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic Isopropyl alcohol, 5%. v The above proportions are all weight percents. Having thus described my invention, what I claim as new and desire to secure by Letters Patent is:

l. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile productsbeing acidic fractional esters obtained by the manufacturing process of esterifying (A) an oxyalkylated amine-modified phenol-aldehyde resin condensate with (B) a polycarboxy acid; said oxyalkylated condensate being obtained by the process of first condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and notover 6 phenolic nuclei per resin molecule; said resin being difunctional-only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over'8 carbon atoms and reactive toward said petroleum solvent, 15%;

phenol; said resin being formed in the substantial vab- I sence of tri-functional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more 24 carbon atoms and substituted .in the 2,4,6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at I as polycarboxy acid reactant to oxyalkylated reactant being one mole of the former for each hydroxyl group present in the latter.

2. A process for breaking petroleum emulsions of thewater-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being acidic fractional esters obtained by the manufacturing process of esterifying (A) an oxyalkylated aminephenol and an aldehyde'having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having in;the substantial absencebf trifunctional phenols; said I phenol being of the formula v in an aliphatic hydrocarbon radical having cut at least one basiQ-Secondary amino radical and charat least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is pres-- cut at least one basic secondary amino radical and characterized by freedom from any primary amino radical;

and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and 'resultants of reaction; with the provisothat the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the'three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting theamino nitrogen atom of reaction with a oxyalkylation-susceptible; followed by an oxyalkylati on resin molecule; with the further proviso that the ratio stepby means of an alpha-beta-alkylene oxide having not more than 4 carbon atoms and selected from the classconsisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; the ratio of polycarboxy acid reactant to oxyalkylated reactant being one mole of the former for each hydroxyl group present in the latter.

3. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being acidic fractional esters obtained by the manufacturing process of esterifying (A) an oxyalkylated aminemodified phenol-aldehyde resin condensate with (B) a polycarbox'y acid; said oxyalkylated condensate being obtained by the process of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyderesin having an average molecular weight corresponding to atleast 3 and not over '6 phenolic nuclei resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said'resin being formed acte riz d ,by freedom from any primary amino radical; and (c){tormaldehydgsaid condensation reaction being conducted ata temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the-resultant in which each of the three reactants have contributed part of the ultimate molecule; by virtue-eta formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ratio of reactants beap'proximately 1,2 and 2, respectively; 'with thefurther-proviso "that 'saidprocedure involve the -use of a solvent; "and with the final proviso that the resinouscondensation product resulting 'from the process beheat-stable and oxyalkylation-susceptible; followed by 'an oxyalkylationstep' by means of an alpha-beta alkylene 'oxid'e havingn'ot morelthan 4 carbon atoms and selected from the; classconsi sting of ethylene oxide, propylene oxide," butylene-oxide, glycide. and methylglycide; the ratio of polycarboxy acid reactant to oxyalkylated reactant being one mole of the former for each hydroxyl group present in=the latter. v

4."A"pr'ocessfor brcakingpetroleum emulsions of the -water+in-oil typ'e' characterized by subjecting the emulsion to the action oft-a demulsifier including synthetic hydrophile products; :s'aidsynthetic hydrophile products being acidic" fractionalI'esters obtained by the manufacturing process v of esterifying (A) an oxyalkylated aminemodified.phenol-aldehyde'resin condensate with (B) a polycarboxy'acid; said .oxyalkylated condensate being obtained" byithe i process of v.first condensing (a) an oxyalkylation susceptible;fusible, non-oxygenated organic solvent-soluble,Ewwateninsoluble, low-stage phenol-formaldehyde. resinhavingan average molecular weight cor responding to at least 3 and not over 6 phenolic nuclei per resin'moleeule;:;said resin being difunctional only in regard to imethylolforming reactivity; [said resinb'eing derived by reaction between a difunctional monohydric phenol and lforinaldehydm' said resin being derived 'by reaction bet-ween a difunctional monohydric phenol and formaldehyde; said resin beingformed in the substantial absence,oftrifunctional phenols; said phenol being of the formulaf j in I which an aliphatic hydrocarbon radical having at least 4 and notmore than 24 carbon atoms and substituted inthe 2,4,fi position; (b) cyclic amidines selected 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING SYNTHETIC HYDROPHILE PRODUCTS; SAID SYNTHETIC HYDROPHILE PRODUCTS BEING ACIDIC FRACTIONAL ESTERS OBTAINED BY THE MANUFACTURING PROCESS OF ESTERIFYING (A) AN OXYALKYLATED AMINE-MODIFIDE PHENOL-ALDEHYDE RESIN CONDENSATE WITH (B) A POLYCARBOXY ACID; SAID OXYALKYLATED CONDENSATE BEING OBTAINED BY THE PROCESS OF FIRST CONDENSING (A) ANOXYALKYLATION SUSCEPTIBLE, FUSIBLE NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRI-FUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 